Azo compounds containing an arylsulfonyl phenyl diazo component

ABSTRACT

Azo compounds having the general formula IN WHICH EACH OF R1 and R2 is a conventional diazo component substituent or the group -SO2-R3, R3 is an aryl group, and A is the residue of a disperse dye aniline or tetrahydroquinoline coupling component which bears an acylamido group on a ring carbon atom ortho to the azo group. The azo compounds produce reddish-blue to greenish-blue shades on polyester fibers and exhibit good dyeability, fastness to light and resistance to sublimation.

United States Patent Weaver et al.

[ 51 Sept. 19, 1972 1 AZO COMPOUNDS CONTAINING AN ARYLSULFONYL PHENYL DIAZO COMPONENT [72] Inventors: Max A. Weaver, Route 8, Kingsport, Tenn. 37664; James M. Straley, Route 10, Kingsport, Tenn. 37663 [22] Filed: Feb. 18, 1970 [21] App1.No.:12,438

[56] References Cited UNITED STATES PATENTS 2,151,857 3/1939 Manz et a1. ..260/205 2,397,927 4/ 1946 Dickey et a1 ..260/207.l X 2,436,100 2/1948 Dickey ..260/207 2,873,270 2/1959 Merian ..260/205 2,967,858 1/1961 Merian et a1. ..260/205 3,359,256 12/1967 Mueller et a1 ..260/206 X 3,398,137 8/ 1968 Mueller ..260/207 3,406,164 10/ l 968 Altermatt et a1. ..260/207 3,417,076 12/1968 Sartori ..260/205 3,428,622 2/ 1969 Altermatt et a1. ..260/207 3,483,180 12/1969 Ramanathan ..260/158 2,529,924 11/1950 Dickey ..260/155 2,746,952 5/1956 Dickey et a1 ..260/155 3,386,990 6/1968 Dale et al. ..260/155 Primary Examiner-Floyd D. Higel Attorney-J. Frederick Thomsen and Cecil D. Quillen, Jr.

[57] ABSTRACT Azo compounds having the general formula R --N=N-A in which each of R and R is a conventional diazo component substituent or the group SO,--R R is an aryl group, and A is the residue of a disperse dye aniline or tetrahydroquinoline coupling component which bears an acylamido group on a ring carbon atom ortho to the azo group. The azo compounds produce reddish-blue to greenish-blue shades on polyester fibers and exhibit good dyeability, fastness to light and resistance to sublimation.

8 Claims, No Drawings AZO COMPOUNDS CONTAINING AN ARYLSULFONYL PHENYL DIAZO COMPONENT This invention relates to certain novel azo compounds and, more particularly, to certain azo compounds and to polyester textile materials dyed with the novel compounds.

The novel compounds of the invention have the formula (I) S O2-B wherein R is nitro, cyano, lower alkylsulfonyl, R -SO trifluoromethyl, lower alkoxycarbonyl, carbamoyl,

lower alkylcarbamoyl, di-lower alkylcarbamoyl, sulfamoyl, lower alkylsulfamoyl or di-lower alkylsulfamoyl;

R is nitro, cyano, lower alkylsulfonyl, lower alkoxycarbonyl, aroyl, carbamoyl, lower alkylcarbamoyl, dilower alkylcarbamoyl, arylazo, or SO R R is an aryl radical; and

A is a p-aminophenyl or l,2,3,4-tetrahydroquinol-6- yl coupling component bearing an acylamido group ortho to the azo groups.

The novel azo compounds produce bright reddishblue to greenish-blue shades on hydrophobic textile materials such as polyester fibers. The novel compounds possess excellent fastness to light and resistance to sublimation. The excellent dyeability properties, e.g. build-up and affinity, possessed by the novel com pounds permits their application onto polyester fibers by either exhaustion, including atmospheric pressure, and thermal fixation dyeing techniques. As used herein to describe a group containing an alkyl moiety, lower designates a carbon content of up to about four carbon atoms.

The coupling components which, in formula (I), are represented by A have the formula wherein X is -CO, -COO, or SO R is lower alkyl, cycloalkyl, aryl, lower alkylamino, di-lower alkylamino, or arylamino; R is hydrogen, lower alkyl, lower alkoxy, aryloxy, lower alkylthio, or arylthio; R is an alkyl radical having from one to about eight carbon atoms or cycloalkyl; R is hydrogen or an alkyl radical which R can represent, and R R and R are the same or different and each is hydrogen or lower alkyl. Preferably, R and R each is hydrogen or methyl and both are hydrogen when R is alkyl of two to four carbon atoms.

Methylsulfonyl, ethylsulfonyl, propylsulfonyl, n-butylsulfonyl, isobutylsulfonyl, methoxycarbonyl, ethoxycarbonyl, isopropoxycarbonyl, and butoxycarbonyl ycarbonyl,

are typical alkylsulfonyl and alkoxycarbonyl groups represented by R and R Ethylcarbamoyl, butylcarbamoyl, dimethylcarbamoyl, diethylsulfamoyl, propylsulfamoyl and isobutylsulfamoyl are examples of the substituted carbamoyl and sulfamoyl groups represented by R and R The aryl groups represented by R and R, the aryl moiety of the aroyl groups, i.e. arylcarbonyl, represented by R and other aryl groups present on the novel azo compounds can be unsubstituted phenyl or phenyl bearing substituents such as lower alkyl, lower alkoxy, halogen, nitro, cyano, lower alkanoylamino or lower alkoxycarbonyl. Examples of such groups include phenyl, phenoxycarbonyl, p-tolyl, m-nitrophenyl, p-anisyl, o,p-dimethoxyphenyl, pethylphenyl, m-butylphenyl, p-cyanophenyl, p-methoxycarbonylphenyl, 0,p-dichlorophenyl, o-bromo-p-tolyl, p-acetamidophenyl, p-butyramidophenyl, etc.

The lower alkyl groups represented by R can be unsubstituted or substituted, for example, with halogen, phenyl, cyano, lower alkoxy, lower alkylsulfonyl, hydroxy, lower alkylthio, lower alkanoyloxy, etc. Cyclohexyl and lower alkylcyclohexyl are representative cycloalkyl groups represented by R. Methylamino, ethylamino, and butylamino are typical alkylamino groups which R can represent. The aryl groups represented by R and the aryl component of the arylamino groups represented by R are defined hereinabove. Acetyl, propionyl, butyryl, cyanoacetyl, chloroacetyl, bromoacetyl, trifluoroacetyl, phenylacetyl, methoxyacetyl, ethylthioacetyl, methylsulfonylacetyl, methoxycarbonyl, propoxycarbonyl, butoxycarbonyl, methylsulfonyl, ethylsulfonyl, propylsulfonyl, butylsulfonyl, 2-cyanoethylsulfonyl, 2-methoxyethylsulfonyl, 2-chloroethylsulfonyl, cyclohexoyl, 4-.

ethylcyclohexoyl, benzoyl, 4-ethylbenzoyl, 3- nitrobenzoyl, 4-cyanobenzoyl, 4-ethoxycarbonylbenzoyl, phenoxycarbonyl, 2,4-dichlorophenoxycarbonyl, 4-bromophenoxycarbonyl, 4-acetamidophenoxbenzenesulfonyl, p-toluenesulfonyl, 4-

v propionamidophenylsulfonyl, 4-chlorophenylsulfonyl,

cyclohexoxycarbonyl, 4-butylcyclohexylsulfonyl, ethylcarbamoyl, butylsulfamoyl, phenylcarbamoyl, p-tolylcarbamoyl, p-anisylcarbamoyl, and phenylsulfamoyl are typical groups represented by XR.

Examples of the alkyl and alkoxy groups which. R can represent are described in the preceding paragraphs. Phenoxy, p-tolyloxy, p-ethoxyphenoxy, methylthio, ethylthio, butylthio, phenylthio, macetamidophenylthio, p-chlorophenylthio and mnitrophenylthio are typical aryloxy, alkylthio and arylthio groups represented by R The alkyl radicals represented by R and/or R" can be unsubstituted or substituted, straightor branchchain alkyl. Methyl, ethyl, propyl, isopropyl, butyl, isobutyl, hexyl, 2-ethylhexyl and 1,3-dimethylbutyl are typical unsubstituted alkyl groups. Examples of the substituents which can be present on those alkyl groups are hydroxy, cyano, lower alkoxy, lower cyanoalkoxy, dicarboximido, such as succinimido, glutarimido and phthalimido; aryl, aryloxy, and arylcarbamoyloxy in which the aryl groups are any of those described hereinabove; piperidono, pyrrolidinono, phthalimidino, cyclohexyl, lower alkylcyclohexyl, lower alkylcarbamoyloxy, carbamoyl, furyl, etc. The groups represented by RX, R -X- NH-, ROOCO- and R--COO also can be present on the alkyl groups represented by R and R The substituted alkyl groups preferably are substituted lower alkyl. Specific examples of the substituted alkyl groups which R and/or R" can represent include 2- hydroxyethyl, 2,3-dihydroxypropyl, 3-chloro-2-hydroxypropyl, 2-bromoethyl, 3-chloropropyl, 2-cyanoethyl, 2-ethoxyethyl, 4-methoxybutyl, 2-(2-cyanoethoxy)ethoxy, Z-acetoxyethyl, 2,3-dipropionoxypropyl, 2- succinimidoethyl, 3-phthalimidopropyl, benzyl, 4- methoxycarbonylbenzyl, 2-(4-ethoxyphenyl)ethyl, 4- chlorobenzyl, 2-phenoxyethyl, 3-(4-acetamidophenoxy)propyl, 2-phenylcarbamoyloxyethyl, 2-(2-pyrrolidinono)ethyl, 3-(2-piperidono)propyl, 2- phthalimidinoethyl, 2-acety1ethyl, 4-propionylbutyl, 2- ethoxycarbonylethyl, 2-carbamoylethyl, 3-isopropylcarbamoylpropyl, cyclohexylmethyl, 3-(3-ethylcyclohexyl)propyl, furfuryl, 2-methylsulfonylethyl, 2- sulfamoylethyl, 3-butylsulfamoylpropyl, 2phenylsulfonylethyl, 2-(4-ethylbenzoyl)ethyl, 2-p-toloyloxyethyl, 2-acetamidoethyl, 2-methylsulfonamidoethyl, 3-benzamidopropyl, 2-ethoxycarbonyloxyethyl, 3- benzoyloxypropyl, etc. Cyclohexyl and lower alkylcyclohexyl are typical cycloalkyl groups which R can represent.

Dyeings of excellent depth and having exceptional fastness properties on polyester fibers can be obtained economically with a compound having the general formula wherein R is phenyl, tolyl or anisyl; Y is lower alkanoyl, lower alkylsulfonyl, lower alkoxycarbonyl, benzoyl, or lower alkylcarbamoyl, R is hydrogen, methyl, methoxy or ethoxy; R is alkyl having one to about eight carbon atoms or lower alkyl substituted with hydroxy, lower alkoxy, lower alkanoyloxy, lower alkylsulfonyl, cyano, phenyl, lower alkanoylamino, lower alkoxycarbonylamino, or lower alkylsulfonamido; R is hydrogen, alkyl having from one to about eight carbon atoms, or lower alkyl substituted with hydroxy, lower alkanoyloxy, or lower alkoxy; R and R each is hydrogen or methyl; and R is hydrogen, methyl, or, when R and R each is hydrogen, alkyl of two to four carbon atoms. In addition to their excellent fastness properties, the desirable blue shade produced by these compounds also renders them particularly valuable polyester dyes.

The novel compounds are prepared by reacting a compound having the formula wherein R, R and A are defined above except that R cannot represent R -SO with a benzenesulfinic alkali salt having the formula R SO Z, wherein Z is sodium or potassium, in the presence of an inert solvent such as N,N-dimethylformamide. When R is not nitro, reaction of an azo compound of formula (II) with R SO Z yields the corresponding compound in which the bromine atom is replaced with SO R If R is nitro, reaction of compound (II) with at least two equivalents of R SO -Z gives the corresponding 2,6di---SO R compound. The presence of a small amount of cuprous bromide in the reaction of a compound of formula (I), in which R is nitro, produces the analagous 2-nitro-6-SO -R compound. Completion of the displacement reaction and the structure of the azo product is established by thin-layer chromotography and/or elemental analysis. Some of the compounds of formulas (II) and (III) are known compounds. However, those known compounds do not possess the resistance to sublimation possessed by the novel compounds of the invention. The good yields in which the novel azo compounds can be synthesized is another desirable feature of applicants compounds. Although certain known azo compounds having a 2-cyano-4,6- dinitrophenyl diazo component and coupling component A produce desirable blue shades on polyester fibers, such azo compounds cannot be obtained in good yields and/or purity. The azo compounds having formulas (II) and (Ill) can be prepared by diazotizing an aniline compound having the formula and coupling the resulting diazonium salt to a coupler having the formula l-lA according to conventional procedures. The aniline compounds and the couplers are known and/or can be synthesized according to known techniques.

The novel azo compounds and their preparation and use are further illustrated by the following examples.

EXAMPLE 1 EXAMPLE 2 The procedure described in Example 1 is repeated using 0.8 g. of 4-(2-bromo-6-cyano-4-nitrophenylazo)- N,N-diethyl-3-acetamidoaniline, 0.3 g. sodium benzenesulfinate, and [5 ml. dimethylformamide. The blue azo compound obtained, 4-(2-cyano-4-nitro-6- phenylsulfonylphenylazo)-N,N-diethyl-3- acetamidoaniline, exhibits outstanding fastness to light and resistance to sublimation when applied to cottonpolyester blends by the heat fixation dyeing technique.

EXAMPLE 3 1.35 g. 4-(2-Bromo-4,6-dinitrophenylazo)-N-benzyl- N-ethyl-3-acetamidoaniline, 0.55 g. sodium benzenesulfinate, and 15 ml. dimethylformamide are heated together on a steam bath for about 20 minutes. A sample of the reaction mixture reveals two products, indicating that both the ortho-nitro and orthobromo groups are being displaced. Upon addition of 0.55 g. additional sodium benzenesulfinate and heating for another hour, only one product is obtained. This azo compound, 4-(4-nitro-2,6-diphenylsulfonylphenylazo)- N-benzyl-N-ethyl-3-acetamidoaniline, produces a blue shade on polyester fibers.

Anal. Calcd. for C H ,N S S, 9.19; N, 10.04

Found: S, 9.19; N, 9.80

EXAMPLE 4 1.0 g. of 4-(2-Bromo-4,6-dinitrophenylazo)-N,B- benzoyloxyethyl-N-ethyl 3-acetamidoaniline, 0.32 g. sodium benzenesulfonate, 0.1 g. cuprous bromide and 25 ml. dimethylformamide are heated for 30 minutes on a steam bath. The reaction mixture is drowned in water and the product is filtered off, washed with water and air dried. The azo product, 4-(-2,4-dinitro-6-phenylsulfonylphenylazo)-N,B-benzoyloxyethyl-N-ethyl-3- acetamidoaniline, produces fast blue shades on polyester fibers.

EXAMPLE 5 YA mixture of the azo compound 6-(2-bromo-6- cyano-4-nitrophenylazo)-N,Bacetoxyethyl-7- acetamido-2,2,4-trimethyl-l ,2,3,4-tetrahydroquinoline (0.4 g.), sodium benzenesulfinate (0.2 g.), and dimethylformamide ml.) is heated on a steam bath (95-100C.) for minutes. The resulting azo compound, 6-(2-cyano-4-nitro-6-phenylsulfonylphenylazo)-N,Bacetoxyethyl-7-acetamido-2,2,4-trimethyll,2,3,4-tetrahydroquinoline, produces bright blue shades exhibiting excellent fastness properties on polyester fibers.

EXAMPLE 6 The procedure of Example 5 is repeated using 1.0 g. of 6-(2-bromo-6-cyano-4-nitrophenylazo)-7- acetamido-N,B-benzoyloxyethyl-Z,2,4-trimethyll,2,3,4-tetrahydroquinoline, 0.5 g. sodium benzenesulfinate, and ml. of dimethylformamide. The azo compound obtained, 6-(2-cyano-4-nitro-6-phenylsulfonylphenylazo)-7-acetamido-N,B-benzoyloxyethyl- 2,2,4-trimethyl-l,2,3,4-tetrahydroquinoline produces blue shades and exhibits excellent lightand sublimation-fastness on polyester fibers.

The azo compounds described in Tables I and 11 are prepared according to the procedures described in Examples 1 through 6. The azo compounds of Table l conform to the general formula and those of Table II conform to the formula The compounds disclosed in the Examples of Tables I and 11 produce bright shades of reddishto greenishblue on polyester fibers.

The compounds of the invention can be applied to linear polyester textile materials in accordance with known disperse dyeing procedures using auxiliary dyeing agents such as surfactants, dispersing agents, carriers, thickeners, etc. The dyeing can be carried out at the boil at atmospheric pressure or at higher temperatures under a pressure moderately above atmospheric pressure. The following example illustrates a carrier dyeing procedure for applying the az'o compounds of the invention to polyester textile materials.

EXAMPLE. 183

The azo compound of Example 11 (0.1 g.) is dissolved in 10 cc. of 2-methoxyethanol. A small amount (3-5 cc.) of a 3 percent sodium lignin sulfonate aqueous solution is added, with stirring, and then the volume of the bath is brought to 300 cc. with water. 3 cc. of a solvent carrier (Tanavol) is added to the bath and 10 g. of a textile fabric made of poly(ethylene terephthalate) fibers is placed in the bath and worked 10 minutes without heat. The dyeing is carried out at the boil for one hour. The dyed fabric is removed from the dyebath and scoured for 20 minutes at C. in a solution containing 1 g./l. neutral soap and 1 g./l. sodium carbonate. The fabric is then rinsed, dried in an oven at 250F. and heat set (for removal of residual carrier) for 5 minutes at 350C. The fabric is a bright shade of blue which exhibits excellent fastness to light.

The compounds of the invention can also be applied to polyester textile materials by the heat fixation technique described in U.S. Pat. No. 2,663,612 and in the American Dyestuff Reporter, 42, l (1953). The following procedure describes how the azo compounds of the invention can be applied to polyester materials by the heat fixation technique.

EXAMPLE 184 A mixture of:

500 mg. of the compound of Example 9, 150 mg. ofa sodium lignosulfonate dispersing agent (Marasperse N), 150 mg. of a partially desulfonated sodium lignosulfonate (Marasperse CB), 0.5 ml. glycerin, and 1.0 ml. of water is ground in a micro-size container (an accessory for a l-quart size Szegvari Attritor) for approximately 3.5 hours. Enough 56-inch stainless steel balls are added to provide maximum grinding. When the grinding is complete, the entire contents are poured into a beaker and ml. of water are used to wash the remaining dye paste from the micro-container. The dye paste is then heated slowly to 65C. with continuous stirring. A thickener and penetrating mixture is prepared by mixing 1 ml. of a complex diaryl sulfonate (Compound 8-S), 3 ml. of a 3 percent solution of a sodium N-methyl-N-oleoyl-taurate (lgepon T-Sl), 8

ml. of a 25 percent solution of natural gums (Superclear SON), and sufficient water to bring the volume to 100 ml. The thickener and penetrating mixture is added to the dye paste, the volume is adjusted to 200 ml. and the mixture is agitated for l5 minutes. The dye mixture is then filtered through folded cheesecloth to remove the stainless steel balls and it then is added to the resevoir of a Butterworth padder where it is heated to about 4560C.

g. of a fabric of poly(ethylene terephthalate) fibers and 10 g. of a fabric of 65/35 spun poly(ethylene terephthalate)/cotton fibers are sewn together, end-toend, and padded for 5 minutes of continuous cycling through the dye mixture and between three rubber squeeze rollers of the padder. Dye mixture pick-up is about 60 percent based on the weight of the fabrics. The padded fabrics are then dried at 200F. and then heat-fixed for 2 minutes at 415F. in a forced air oven.

The dyed fabrics are scoured for minutes at 65-70 C. in a solution containing 0.2 percent sodium hydrosulflte, 0.2 percent sodium carbonate and L7 percent of a 3 percent solution of sodium N-methyl-N- oleoyltaurate and then dried. The dyed fabric possesses excellent brightness and fastness to light and sublimation when tested according to the procedures described in the 1968 edition of the Technical Manual of the American Association of Textile Chemists and Colorists.

The heat fixation dyeing procedure described above can be varied by the substitution of other dispersing agents, surfactants, suspending agents, thickeners, etc. The temperature and time of the heat-fixation step can also be varied.

Polymeric linear polyester materials of the terephthalate sold under the trademarks Kodel, Dacron" and Terylene are illustrative of the linear aromatic polyester textile materials that can be dyed with the compounds of our invention. Examples of linear polyester textile materials that can be dyed with the compounds of the invention are those prepared from ethylene glycol and dimethylterephthalate or from cyclohexanedimethanol and dimethylterephthalate. Polyesters prepared from cyclohexanedimethanol and dimethylterephthalate are more particularly described in U.S. Pat. No. 2,901,446. Poly(ethylene terephthalate) polyester fibers are described, for example, in U.S. Pat. No. 2,465,319. The polymeric linear polyester materials disclosed in U.S. Pat. Nos. 2,945,010; 2,957,745 and 2,989,363, for example, can be dyed. The linear aromatic polyester I materials specifically named have a melting point of at least 200C. The poly(ethylene terephthalate) fibers which are dyed with the compounds of the invention are manufactured from a melt of a polymer having an inherent viscosity of at least 0.35 and preferably, about 0.6. The inherent viscosity of the poly(l,4-cyclohexylenedimethylene terephthalate) polymer is also at least 0.35. These inherent viscosities are measured at C. using 0.25 g. polymer per 100 ml. of a solvent consisting of 60 percent phenol and 40 percent tetrachloroethane. The polyester fabrics, yarns, fibers and filaments that are dyed with the novelazo compounds can also contain minor amounts of other additives such as brighteners, pigments, delusterants, inhibitors, stabilizers, etc. Although the azo compounds of the invention are particularly suitable for dyeing polyester textile materials, they can also be'used to dye other hydrophobic textile materials such as cellulose acetate and polyamide fibers.

The invention has been described in considerable detail with particular reference to preferred embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention.

We claim:

1. A compound having the formula wherein R is nitro, cyano, lower alkylsulfonyl, R -SO trifluoromethyl, lower alkoxycarbonyl, carbamoyl, lower alkylcarbamoyl, di-lower alkylcarbamoyl, sulfamoyl, lower alkylsulfamoyl, or di-lower alkylsulfamoyl;

R is nitro, cyano, lower alkylsulfonyl, R SO lower alkoxycarbonyl, aroyl, carbamoyl, lower alkylcarbamoyl, di-lower alkylcarbamoyl, or arylazo;

R is aryl;

R is lower alkyl; lower alkyl substituted with halogen, phenyl, cyano, lower alkoxy, lower alkylsulfonyl, hydroxy, lower alkylthio, lower alkanoyloxy, lower alkanoylamino, N-lower alkyllower alkylsulfonamido, lower alkanoyl, or cyclohexyl; cyclohexyl; lower alkylcyclohexyl; aryl; lower alkylamino; di-lower alkylamino or; arylamino;

R is hydrogen, lower alkyl, lower alkoxy, aryloxy,

lower alkylthio, or arylthio;

R is alkyl of from one to about eight carbon atoms; lower alkyl substituted with hydroxy, cyano, lower alkoxy, lower cyanoalkoxy, aryl, aryloxy, arylcarbamoyloxy, alkylcarbamoyloxy, cyclohexyl, lower alkylcyclohexyl, carbamoyl, R"-X, RX- NH-, R OOCO-, or R-COO; cyclohexyl; or lower alkylcyclohexyl; and

R is hydrogen or an alkyl radical conforming to the definition of R wherein each aryl group is phenyl or phenyl substituted with lower alkyl, lower alkoxy, halogen, nitro, cyano, lower alkanoylamino, or lower alkoxycarbonyl.

2. A compound according to claim 1 having the formula sol-m R5 l cN NH-Y wherein R is phenyl, tolyl, or anisyl; Y is lower alkanoyl or, lower alkoxycarbonyl, R is hydrogen, methyl, methoxy, or ethoxy;

R is alkyl having one to about eight carbon atoms;

l 7 L6 lower alkyl substituted with hydroxy, lower alkoxy, 6. A compound according to claim I having the forlower alkanoyloxy, lower alkylsulfonyl, cyano, mu a phenyl, lower alkanoylamino, lower alkoxycarbonylamino, or lower alkylsulfonamido; or cyclohexyl; and R is hydrogen, alkyl having one toabout eight 5 b02 oHgomoN carbon atoms, or lower alkyl substituted with o zN- N=N- N hydroxy, lower alkanoyloxy, or lower alkoxy. 3. A compound according to claim 1 having the for- N gIHCOCH: CHZCHQOH mula so 2- 7. A compound according to claim 1 having the for- GHQCHQCHQCHQ mula OzN N=NN\ CHQCHOHa JEN NHCO CH3 l Q OH soi- CH;

4. A compound according to claim 1 having the formula I N NHCOCH:

/CII2OH2OOCCII3 h f OQN 8. A compound according to claim 1 having t e ormula J: I C2115 N NHCO CH2 5. A compound according to claim 1 having the for- CH3 1 l mu a /CH: HCH3 C2H5 v cmomomon N=N N N Nncoom g H l CzHs N NHC 0 CH:

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTICN Patent 3,592,769 7 Dated September 19, 19772 Inventor(s) Max A. Weaver et a1 It is certified that error appears in 'the above-identified patent and that said Letters Patentare hereby corrected as shown below:

On the cover sheet insert [73] Assignee Eastman Kodak Company, Rochester, New York Signed and sealed this 1st day of May 1973.

(SEAL) Attest:

EDWARD M.FLETCHER,JR. ROBERT GOTTSCHALK Attesting Officer Commissioner of Patents Q VM O-1050 (10 69) USCOMM-DC 60876-P69 fr u.s. GOVERNMENT PRINTING OFFICE: I969 0-366-334,

Notice of Adverse Decision in Interference In Interference No. 98,776 involving Patent No. 3,692,769, M. A. Wea and J. M. Stan-lay, AZO COMPOUNDS CONTAINING AN ARYLSUL- FONYL PHENYL DIAZO COMPONENT, final judgment adverse to the patentees was rendered Oct. 20, 1975, as to claims 1, 2 and 5.

[Ofiicial Gazette Febmmy 10, 1976.] 

2. A compound according to claim 1 having the formula wherein R3 is phenyl, tolyl, or anisyl; Y is lower alkanoyl or, lower alkoxycarbonyl, R5 is hydrogen, methyl, methoxy, or ethoxy; R6 is alkyl having one to about eight carbon atoms; lower alkyl substituted with hydroxy, lower alkoxy, lower alkanoyloxy, lower alkylsulfonyl, cyano, phenyl, lower alkanoylamino, lower alkoxycarbonylamino, or lower alkylsulfonamido; or cyclohexyl; and R7 is hydrogen, alkyl having one to about eight carbon atoms, or lower alkyl substituted with hydroxy, lower alkanoyloxy, or lower alkoxy.
 3. A compound according to claim 1 having the formula
 4. A compound according to claim 1 having the formula
 5. A compound according to claim 1 having the formula
 6. A compound according to claim 1 having the formula
 7. A compound according to claim 1 having the formula
 8. A compound according to claim 1 having the formula 